Process for making cellulosic textiles rot resistant with zirconium salts and phenols



United States Patent PROCESS FOR MAKING CELLULOSIC TEXTILES ROTRESISTANT WITH ZIRCONIUM SALTS AND PHENOLS Elwood J. Gonzales, Kenner,and Clark M. Welch and John D. Guthrie, New Orleans, La., assignors tothe United States of America as represented by the SecretaryofAgriculture No Drawing. Filed Sept. 20, 1962, Ser. No. 225,166

22 Claims. (Cl. 16738.7)

(Granted under Title 35, US. Code (1952), see. 266) A non-exclusive,irrevocable, royalty-free license in the invention herein described,throughout the world for all purposes of the United States Government,with the power to grant sublicenses for such purposes, is hereby grantedto the Government of the United States of America.

This invention relates to the bonding of phenolic compounds tocellulosic textiles with zirconium salts. An object of the invention isto produce cellulosic textiles with increased rot resistance. A secondobject is to provide enhanced breaking strength. Other objects willbecome evident from a description of the invention.

It is well known that phenols are highly effective in inhibiting theattack of microorganisms on a given substrate. Heretofore, nosatisfactory method has been devised for durably bonding the phenol to asolid substrate without at the same time destroying the bacteriocidalactivity of the phenol. The present invention utilizes zirconium saltsas the bonding agent. These have the property of undergoing olation inaqueous media to give polymers of the type 0 0 (IIO) Z r r Z r(OH) //\LMoreover, the zirconium salts and their olated polymers have theproperty of forming coordination complexes with phenols and with hydroxycompounds in general (B. I. Intorre and A. E. Martell, J. Am. Chem. Soc.82, 358 (1960)). It is therefore likely that the zirconium salts servein the present invention to form polymers which coordinate both with thephenol and with hydroxyl groups of the cellulose, thus forming a bridgebetween the two. It is found that this mode of bonding does not destroythe ability of the phenol to inhibit attack by microorganisms, andunexpectedly, the tensile strength of the textiles so treated is foundto be increased. The coating obtained has no appreciable effect on thesuppleness of the textile material. Many of the finishes also impartwater repellency to the textile. The treatments are highly durable towashing with hot water and to extraction with hot organic solvents.

The process described herein differs from all previously describedtextile finishing methods that utilize metal salts, hydroxides or oxidesas bonding agents, in that heretofore only those organic materials whichwere chelating agents could be bonded to cellulosic textiles. Thepresent invention applies to phenols in general, including those thatare incapable of forming chelate rings. Monohydric phenols as well aspolyhydric phenols may be applied. Among the phenols most efficientlybound to cellulosic textiles are those whose complexes with zirconiumsalts have a high stability constant, and also those whose complexeswith zirconium salts are insoluble in water. Phenols having very largeand bulky substituents were less efficiently bonded to cellulose. Thepresent invention also is novel in that it permits the bonding of thephenol to the cellulose in amounts up to 10% of the latter by weight, insome cases. Not all phenols are equally effecice tive in imparting rotresistance to cellulose. Halogenated phenols such as pentachlorophenol,pentabromophenol or 2,2-methylenebis(4-chlorophenol) are especiallyactive in inhibiting microbiological attack. Mercurated phenols such asp-hydroxyphenylmercuric chloride also are effective. The phenol may beused directly or as its alkali metal salt.

Although any salt of tetravalent zirconium soluble in water at a pH of 2or higher may be used, the zirconium salt is preferably one derived fromzirconium hydroxide, or zirconyl hydroxide, and a volatile acid havingan acid dissociation constant equal to or less than 5 10- and a boilingpoint equal to or less than 160 C. With zirconium salts or zirconylsalts of strong acids, the acid liberated during the olation processwill degrade and tender the cellulosic textile material. The olationproceeds more nearly to completion, the more readily the acid is removedby volatilization. Examples of suitable salts are zirconium acetate,zirconyl acetate and sodium zirconium acetate.

In carrying out the process of this invention, the phenol and thezirconium salt may be applied either together or separately to thecellulosic textile material, followed by drying the textile at 70-170 C.If the phenol and the zirconium salt are applied together, the textilematerial is soaked in a homogeneous solution or an emulsion of thephenol and the zirconium salt in an inert solvent. Solvents suitable forpreparing homogeneous solutions include water and water-miscible organicsolvents such as low-molecular-weight alcohols, ketones, cyclic ethersand amides, as well as mixtures of water with such organic solvents.Vehicles suitable for emulsions may be made from mixtures of water withwater-immiscible inert solvents such as aromatic or aliphatichydrocarbons.

If the zirconium salt and the phenol or the alkali metal salt of thephenol are applied in separate setps, any order of addition may be used,but it is preferable to apply the zirconium salt first. The textilematerial is soaked in an aqueous solution containing 1-25% by weight ofthe zirconium salt, concentrations of 515% being preferable for manypurposes. The cellulosic textile material is subsequently dried eitherby heat or by being allowed to stand at room temperature, after which itis soaked in a solution of the phenol or an alkali metal salt of thephenol dissolved either in water or in any inert organic solvent, suchas an aromatic or aliphatic hydrocarbon, alcohol, ester, ketone orether. The concentration of the phenol or its alkali metal salt to beused will depend on the amount needed in the textile finish, but formost purposes may fall in the range of 05-15%. The textile material issubsequently dried at a temperature of 70170 C.

The materials to which the processes of this invention may be appliedinclude any solid cellulosic material in the form of fiber, yarn, orfabric. Cotton, rayon, ramie, jute, and flax are suitable materials.

The following examples illustrate some of the procedures which may beused and some of the rot-resistant products which can be obtained. Theinvention is not limited to those substances and conditions mentioned inthe examples since the scope of the invention may include many compoundsand variations in procedure not cited. Rot resistance tests were carriedout by ASTM Method D684-45T (AATCC Method 30-4957). Breaking and tearingstrengths were measured in the warp direction, the breaks being made on1" strips. Water repellency was measured by AATCC test method 22-1952.

Example 1 Cotton print cloth x 80) weighing 16.75 grams was soaked in12.5% aqueous zirconium acetate. The fabric was then padded once througha laboratory wringer and cured 5 minutes at C. in a forced draft oven.Im-

mediately after curing, the print cloth was soaked in a solution ofgrams pentachlorophenol dissolved in 50 m1. absolute ethanol, againpadded once through the wringer, and cured minutes at 135 C. in theoven. The swatch was extracted minutes at the boil with ethanol, rinsedonce with this solvent, oven-dried and air-equilibrated overnight. Thefabric showed a 9.4% increase in Weight and contained 0.70% chlorine.Its breaking strength was 10% greater than for untreated fabric. Its rotresistance, as compared with controls treated as above but omitting oneof the reagents and also omitting the extraction step was as follows:

Example 2 The procedure of Example 1 was repeated using 95% ethanol asthe solvent for the pentachlorophenol, and omitting the ethanolextraction of the treated fabric. The weight gain was 14.5%, thechlorine content was 3.48%, and the ash content was 6.04%. The fabrichad a breaking strength of 63.3 lbs. (thread count86) and an E1- mendorftear strength of 750 g. Moderate water repel lency was indicated by aspray rating of 50. The untreated fabric was the same as used in Example1, having a breaking strength of 54.3 lbs. (thread count82) and atearing strength of 1034 g.

The treated fabric retained a breaking strength of 53.1 lbs. after 10weeks burial and 18.5 lbs. after 12 weeks burial. Data for controlfabrics are given in Example 1.

Example 3 The procedure of Example 2 was repeated except that theconcentration of pentachlorophenol was tripled and the treated fabricwas extracted with boiling 95% ethanol for 15 minutes. The fabric showeda weight increase of 13.9%, a chlorine content of 0.39% and an ashcontent of 7.78%. The breaking strength of 67.7 lbs. decreased to 14 and5.2 pounds after the fabric was in the rot bed 7 and 8 weeks,respectively. Data for control fabrics are given in Example 1.

Example 4 A 13.80 g. sample of 80 x 80 print cloth was soaked in 12.5%aqueous zirconium acetate, padded once through a laboratory wringer andcured 5 minutes in a forced-air oven at 135 C. The cured fabric was thenimmediately treated with a 6.8% solution of sodium pentachlorophenate,padded once as above and cured 10 minutes at 135 C. in the oven. Washing5 minutes each in cold and hot running tap water, oven-drying, andallowing the fabric to equilibrate overnight, produced a light tan clothhaving 19.8% weight increase, 3.32% chlorine, 7.53% total ash, and a 50spray rating. Breaking and Elmendorf tear strengths were 63.2 lbs.(thread count 86) and 693 g., respectively. After 7 weeks soil burial,the breaking strength was reduced to 21.5 lbs. after 10 weeks thestrength fell to 12.2 lbs. This treatment may be compared with thezirconium acetate control given in Example 1 and also with a sodiumhydroxide-zirconium acetate control prepared as follows: print cloth wastreated with 12.5% zirconium acetate and cured as above. The cloth wassubsequently steeped in a 3.2% aqueous sodium hydroxide, wrung asbefore. cured 10 minutes at 135 C. in the oven, water-washed as above,oven-dried and air cquilibratcd. The following properties were 4 noted:11.3% add-on, 8.40% ash, a breaking strength of 63.6 lbs., and anElmendorf tearing strength of 740 g. After only 10 days in the rot bed,the breaking strength decreased to 2.3 lbs. The test and controls showthat the sodium pentachlorophenate was bonded to fabric and imparted rotresistance to it.

Example 5 Print colth x 80) was steeped in 12.5% aqueous zirconiumacetate, padded once through the wringer, and cured as before. The curedfabric was then soaked in a 6.1% solution of pentachlorophenolcontaining excess sodium hydroxide (3 g. of the phenol was added to 15ml. 10% aqueous sodium hydroxide and the precipitated sodium saltdissolved with stirring in 30 ml. distilled water), wrung once as above,cured 10 minutes at 135 C., water-washed, oven-dried, and equilibratedovernight. A very light tan fabric, possessing a good hand, 0 sprayrating and 11.7% weight gain was obtained. Soil burial disintegrated thematerial in 3 weeks. Breaking and tear strength were originally 66.3lbs. (thread count-87) and 750 g., respectively. Analyses indicated0.28% chlorine and 7.46% total ash content. This treatment may becompared to the controls cited in Example 4 and Example 1.

Example 6 Print cloth (80 x 80) was treated with 12.5% aqueous zirconiumacetate, put through a wringer to give a 117% wet pickup, and cured 5minutes in the oven at 135 C. In a second step the fabric was soaked ina 10.3% aqueous solution of sodium pentachlorophenate and put through awringer to give a wet pickup of 148%. It was cured at 135 C. for 10minutes. After the second curing step, 200 ml. of 0.1 N HCl was used tosoak the swatch for 5 minutes. The fabric was washed 5 minutes each incold and hot running tap water and was ovendried. Properties obtainedwere a weight gain of 19.5%, 50 spray rating, slight phenolic odor, fairto good hand, light tan color, 5.08% ash content, 5.52% chlorinecontent, Elmendorf tear strength of 760 g. and a thread count of 87. Theoriginal warp breaking strength decreased from 63.3 to 61.3 lbs. on 4weeks soil burial; after 9 weeks burial it was 24.5 lbs. The controlsnoted in Example 4 had much less rot resistance.

Example 7 A 14.05 g. sample of 80 x 80 print cloth was soaked in asolution consisting of 25 ml. n-propyl alcohol, 25 ml. of 25% aqueouszirconium acetate (0.033 mole ZrO and 5 g. (.019 mole)pentachlorophenol. The solution was applied in two dips, two nipsthrough a wringer to a wet pickup. Curing conditions were 10 minutes ina forced-air oven at C. Water-washing, ovendrying, extracting withboiling methanol, and equilibrating overnight gave a fabric having aweight gain of 11.9%, 1.19% chlorine, and 5.92% total ash. The treatmentimparted a good hand and light tan color to the print cloth. TheElmendorf tear strength was 727 g. Soil burial lowered the breakingstrength from 64.7 lbs. (thread count-85) to 45.1 lbs. in 4 weeks andholes were noted in burial strips at 6 weeks. A comparison of observedproperties may be made with the untreated fabric as well as thezirconium acetate and pentachlorophenol-treated controls given inExample 1.

Example 8 An emulsion was prepared by adding 5 g. of pentachlorophenolin 30 ml. xylene to a solution of 25 ml. tap water, 25 ml. 25% aqueouszirconium acetate and 7.5 grams of 35% aqueousN-cetyl-N-ethylmorpholinium ethosulfate, the latter serving as theemulsifying and wetting agent. The mixlnre was agitated in a blender forone minute. The emulsion was padded onto 80 x 80 cotton print cloth intwo dips and two nips through a wringer, resulting in a 103% wet pickup.Curing was t 9.3 lbs.

Example 9 To 3 g. (0.006 mole) pentabromophenol was added 15 ml. 10%aqueous sodium hydroxide (0.038 mole). White flakes of sodiumpentabromophenate which precipitated were redissolved with stirring byaddition of 30 ml. distilled water. The 6.1% solution of the sodium saltwas applied to 80 x 80 cotton print cloth by soaking, padding oncethrough a laboratory wringer and drying 5 minutes in the oven at 135 C.The cloth was subsequently steeped in 12.5% aqueous zirconium acetateand cured minutes in a 135 C. oven. Washing successively in cold and hotrunning tap water for 5 minute periods, oven-drying, and equilibratingovernight gave a fabric having the following properties: light tancolor, good hand, 50 spray rating, 90 flame resistance (by the stripangle test method), 19.9% weight gain, 5.66% bromine, 6.77% ash content,an Elmendorf tear strength of 710 g. and a breaking strength of 65 lb.(thread count -89). The breaking strength remained at 66.5 lbs. after 14weeks soil burial.

Example 10 Print cloth was treated by steeping in a 12.5 aqueouszirconium acetate solution, cured 5 minutes at 135 C. in an oven afterpassing the soaked fabric once through wringer rolls to give a 113% wetpickup. A second bath consisting of a solution of 2.02 grams (0.0075mole) 2,2'-methylenebis(4-chlorophenol) in 50 ml. of 95% ethanol, andcontaining 0.3 ml. of the cationic wetting agent of Example 8, was usedto soak the fabric which was subsequently wrung as above (103% wetpickup) and cured 10 minutes at 135 C.' Washing 5 minutes each in coldand hot running tap water, oven-drying and air equilibrating gave afabric having a 16.1% weight gain, a yellow color, somewhat rough hand,and slight water repellency. It had a breaking strength of 67.8 lbs., anElmendorf tearing strength of 700 g., and contained 6.75% ash as well as1.07% chlorine. Soil burial tests gave the following results forbreaking strength (in pounds): 69.8 after 6 weeks, 61.1 after 11 weeks,57.0 after 12 weeks, 30.5 after 20 weeks. A control in which thezirconium acetate treatment was omitted showed a weight gain of 0.8%, apale yellow color, good hand and no water repellency. Values of 63.1lbs. (thread count-- 85) and 810 g. were observed for the breaking andElmendorf tear strengths, respectively. The fabric contained 0.48%chlorine. The control was observed to rot in just 3 weeks of burial.This shows that the zirconium Cotton print cloth was soaked in 12.5%aqueous zirconium acetate, padded once through a wringer to a 108% wetpickup, and cured in the oven 5 minutes at 135 C. A second treatment wasthen made with a solution composed of 2.02 g. (0.0075 mole)2,2'-methylenebis(4- chlorophenol), 33 ml. 0.91% aqueous sodiumhydroxide (0.0075 mole), 17 ml. distilled water, and 0.3 ml. of thecationic surfactant of Example 8. Padding was performed as in the firststep, giving a 126% wet pickup. Curing was done 10 minutes at 135 C.,followed by washing 5 minutes successively in cold and hot running tapwater, oven-drying, and air-equilibrating overnight. The followingproperties were noted: 16.1% weight gain, a slight degree of waterrepellency, 6.49% ash, 1.49% chlorine, an Elmendorf tear strength of 760g., and a breaking 6 strength of 67.2 lbs. (thread count-88). Thebreaking strength decreased to 63.9 (3 weeks), 50.9 (6 weeks), 15.9 (11weeks) after soil burial.

Example 12 Example 11 was repeated using only half as great aconcentration of zirconium acetate. The weight gain was 10%. The fabricwas lemon-yellow and had a good hand. Analytical data showed the treatedcloth contained 4.04% ash and 1.51% chlorine. The Elmendorf tearstrength was 750 g. and the breaking strength was 69.9 lbs. (87 threadcount). This breaking strength decreased to 66.4, 66.0, 23.8, and 20.2lbs. after 2, 3, 6, and 11 weeks exposure, respectively, tobacteria-inoculated soil.

Example 13 Cotton print cloth was treated by steeping in 12.5% aqueouszirconium acetate, padding once through laboratory squeeze rolls to a112% wet pickup and curing 5 minutes in the oven at 135 C. A second bathwas prepared by diluting 2.02 g. (0.0075 mole) of2,2'-methylenebis(4-ohlorophenol) and 12 m1. 5% aqueous sodium hydroxide(0.015 mole) with 38 ml. of water. A 0.3 ml. quantity of the cationicwetting agent of Example 8 was then added to the resulting solution.Padding as above to a wet pickup, curing 10 minutes at C., washing 5minutes each in cold and hot running tap water, oven-drying andair-equilibrating overnight produced a fabric having 13.6% weight gain,a yellow color, and slight water repellency. The ash and chlorinecontents were 6.88% and 1.15%, respectively. The Elmendorf tear strengthwas 750 g. The original breaking strength of 60.7 lbs. (86 thread count)was unchanged after 6 weeks soil burial. It decreased to 51.3 lbs. at 11weeks and 33.1 lbs. at 14 weeks.

Example 14 Cotton print cloth (80 x 80) was treated by soaking oneminute in a 12.5% aqueous zirconium acetate solution, padding oncethrough a laboratory wringer, and curing 5 minutes in a forced draftoven at 135 C. Immediately after curing, the fabric was again soaked oneminute in a solution of 1.65 g. (0.005 mole) of p-hydroxyphenylmercuricchloride dissolved in 60 ml. tetrahydrofuran, padded as above, and cured10 minutes at 135 C. Extracting the swatch with tetrahydrofuran for 15minutes at the boil, washing 5 minutes successively in cold and hotruning .tap water, and air-drying overnight gave a very pale gray fabrichaving a 13.5% weight gain, and a good hand. The ash content was 6.97%and the chlorine content was 0.046%. The Elmendorf tear strength was 760g. and the breaking strength was 63.9 lbs. (86 thread count). Thetreated fabric after 4 weeks in the rot bed was in good condition.However, the warp breaking strength at 6 weeks was 8.5 lbs. A controlexperiment run in exactly the same manner but omitting thep-hydroxyphenylmercuric chloride showed a 13.6% weight gain, a goodhand, and a 50 spray rating. The ash content was 7.17%, the Elmendorftear strengthwas 1000 g., and the breaking strength was 60.6 lbs. (86thread count). This decreased to 11.1 lbs. in just 2 weeks exposure tosoil-borne microorganisms, showing that the presence ofp-hydroxyphenylmercuric chloride was essential for rot resistance.

Example 15 Print cloth was first treated, padded, and cured withzirconium acetate as in Example 14. In a second step the cured fabricwas soaked 5 minutes in a solution containing 60 ml. distilled water,0.4 g. (0.010 mole) sodium hydroxide, and 1.65 g. (0.005 mole)p-hydroxyphenylminutes at the boil, washing minutes successively in coldand hot running tap water, and air drying was given the fabric. Theweight gain was 12.2%. The resulting fabric, which was white in colorand had a good band, contained 7.07% ash and 0.041% chlorine. TheElmendorf tear strength was 1120 g. Its breaking strength of 66.7 lbs.(86 thread count) decreased to 46.3 lbs. after 6 weeks in the soil bed.The treated cloth remained intact for 9 weeks but rotted at 10 weeks.

Example 1 6 To 30 ml. of 25% aqueous zirconium acetate was added 50 ml.of dimethylformamide and 1.65 grams (0.005 mole) p-hydroxyphenylmercuricchloride. The solid was dissolved with vigorous stirring. Cotton printcloth (80 x 80) was soaked in the nearly colorless solution for oneminute, then passed once through a laboratory wringe-r and cured 10minutes at 135 C. in an oven. The cured fabric was given a minuteafterboil in dimethylformamide prior to-wastu'ng and drying as inExample 15. The weight gain was 10.4%. The fabric was very slightlydiscolored and had a fair hand. The ash content was 5.18% and thechlorine content was 0.042%. The Elmendorf tear strength was 880 g. andthe breaking strength was 67.5 lbs. (87 thread count). A control inwhich only the mercuric compound was omitted in the procedure showed aweight gain of 10.2%. Total ash found was 5.85%. The Elrnendorf tearstrength was 810 g. and the breaking strength was 61.2 lbs. (87 threadcount). The fabric containing the mercury compound resisted rotting bymicroorganisms for 3 weeks but began to decompose at 5 weeks. Thecontrol rotted in only one week.

Example 17 The procedure was similar to that described in Example 16with the exception that tetrahydrofuran was used as the afterboilsolvent. The weight gain obtained was 10.8%. A fairly white color and afair hand were noted. The ash and chlorine contents were 5.49 and0.008%, respectively. The Elmendorf tear strength was 790 g. and thebreaking strength was 64.7 lbs. (84 thread count). The breaking strengthdecreased to 25.6 lbs. after 5 weeks soil burial. Extensive rotting wasnoted at 6 weeks. A control similarly run but with the omission of themercury compound had a 10.6% weight gain and contained 5.84% ash. TheElmendorf tear strength was 820 g. and the breaking strength was 63.5lbs. (thread count86). The control rotted in one week.

We claim:

1. A process for imparting increased rot-resistance,

breaking strength, and water repellency to a cellulosic textile materialwhich comprises treating the cellulosic textile material with reagentsconsisting of from 0.5- 15% by weight of a phenol, from 1-25% by weightof a zirconium salt of a volatile acid the dissociation constant ofwhich is not greater than 5 10 and the boiling point of which is nothigher than 160 C., the balance of the cellulosic textile treatingreagent being a liquid which is chemically inert with respect tocellulose and chemically inert with respect to the said reagents anddrying the treated cellulosic textile material at a temperature of from70-170 C.

2. A process for imparting increased rot-resistance, breaking strength,and water repellency to a cellulosic textile material which comprisestreating the cellulosic textile material with reagents consisting offrom 05-15% by weight of a phenol selected from the group consisting ofpentachlorophenol, pentabromophenol, 2,2'-methylenebis(4-chlorophenol),p-hydroxyphenylmercuric chloride, from l-% by weight of a zirconium saltof a volatile acid the dissociation constant of which is not greaterthan 5 10- and the boiling point of which is not higher than 160 C., thebalance of the cellulosic textile treating reagent being a liquid whichis chemically inert with respect to cellulose and chemically inert withrespect to the said reagents and drying the treated cellulosic textilematerial at a temperature of from -170 C.

3. The process of claim 2 in which the phenol is pentachlorophenol.

4. The process of claim 2 in which the phenol is pentabromophenol.

5. The process of claim 2 in which the phenol is 2,2- methylenebis(4-chlorophenol) 6. The process of claim 2 in which the phenol isphydroxyphenylmercuric chloride.

7. A process for imparting increased rot-resistance, breaking strength,and water repellency to a cellulosic textile material which comprisestreating the cellulosic textile material with reagents consisting offrom 0.5- 15% by weight of the alkali metal salt of a phenol, from 1-25%by weight of a zirconium salt of a volatile acid the dissociationconstant of which is not greater than 5x10" and the boiling point ofwhich is not higher than C., the balance of the cellulosic textiletreating reagent being a liquid which is chemically inert with respectto cellulose and chemically inert with respect to the said reagents anddrying the treated cellulosic textile material at a temperature of from70-170 C.

8. A process for imparting increased rot-resistance, breaking strength,and water repellency to a cellulosic textile material which comprisestreating the cellulosic textile material with reagents consisting offrom 0.5- 15 by weight of the alkali metal salt of a phenol selectedfrom the group consisting of pentachlorophenol, pentabromophenol, 2,2methylenebis-(4-chlorophenol) p -hylroxyphenylmercuric chloride, from125% by weight of a zirconium salt of a volatile acid the dissociationconstant of which is not greater than 5 X 10- and the boiling point ofwhich is not higher than 160 C., the balance of the cellulosic textiletreating reagent being a liquid which is chemically inert with respectto cellulose and chemically inert with respect to the said reagents anddrying the treated cellulosic textile material at a temperature of from70-170 C.

9. The process of claim 8 in which the phenol is pentachlorophenol.

10. The process of claim 8 in which the phenol is pentabromophenol.

11. The process of claim 8 in which the phenol is 2,2- methylenebis(4-chlorophenol) 12. The process of claim 8 in which the phenol isphydroxyphenylmercuric chloride.

13. A process for imparting increased rot-resistance, breaking strength,and water repellency to a cellulosic textile material which comprisestreating the cellulosic textile material with an aqueous mediumcontaining about from 05-15% by weight of a phenol and about from 1-25%by weight of a zirconium salt of a volatile acid the dissociationconstant of which is not greater than 5 X 10" and the boiling point ofwhich is not higher than 160 C., and drying the treated cellulosictextile material at a temperature of about from 70-170 C.

14. The process of claim 13 wherein the phenol is selected from thegroup consisting of pentachlorophenol, pentabromophenol,2,2-methylenebis(4 chlorophenol), and p-hydroxyphenylmercuric chloride.

15. The process of claim 13 wherein the zirconium salt is zirconiumacetate.

16. A process for imparting increased rot-resistance, breaking strength,and water repellency to a cellulosic textile material which comprisestreating the cellulosic textile material with an aqueous mediumcontaining about from 05-15% by weight of a phenol selected from thegroup consisting of pentachlorophenol, pentabromophenol,2,2-methylenebis(4-chlorophenol), and p-hydroxyphenylmercuric chlorideand about from 125% by weight of zirconium acetate, and drying thetreated cellulosic textile material at a temeprature of about from70-170 C.

17. A process for imparting increased rot-resistance,

breaking strength, and water repellency to a cellulosic textile materialwhich comprises treating the cellulosic textile material with an aqueousmedium containing about from 05-15% by weight of an alkali metal salt ofa phenol and about from 1-25% by weight of a zirconium salt of avolatile acid the dissociation constant of which is not greater than5x10- and the boiling point of which is not higher than 160 C., anddrying the treated cellulosic textile material at a temperature of aboutfrom 70-170 C.

18. The process of claim 17 wherein the phenol is selected from thegroup consisting of pentachlorophenol, pentabromophenol,2,2'-methylenebis(4 chlorophenol) and p-hydroxyphenylmercuric chloride.

19. The process of claim 17 wherein the zirconium salt is zirconiumacetate.

20. A process for imparting increased rot-resistance, breaking strength,and water repellency to a cellulosic textile material which comprisestreating the cellulosic textile material with an aqueous mediumcontaining about from 05-15% by weight of an alkali metal salt of aphenol selected from the group consisting of pentachlorophenol,pentabromophenol, 2,2'-methylenebis(4- chlorophenol), andp-hydroxyphenylmeircuric chloride and about from 1-25% by weight ofzirconium acetate, and drying the temperature of about from 70-170 C.

21. The process of claim 20 wherein the alkali metal salt of the phenolis sodium pentachlorophenate.

22. The process of claim 20 wherein the alkali metal salt of the phenolis sodium 'pentabromophenate.

References Cited by the Examiner UNITED STATES PATENTS 2,713,008 7/55Schulenburg 117----138.5 2,762,158 9/56 Dutfey 167--38.6 2,913,369 11/59Haslam 167-30 2,939,164 6/60 Rosenthal 167--30 OTHER REFERENCES Intorreet al.: J.A.C.S., vol. 82, p. 358 (1960).

JULIAN S. LEVI'IT, Primary Examiner.

treated cellulosic textile material at a

1. A PROCESS FOR IMPARTING INCREASED ROT-RESISTANCE, BREAKING STRENTH,AND WATER REPELLENCY TO A CELLULOSIC TEXTILE MATERIAL WHICH COMPRISESTREATING THE CELLULOSIC TEXTILE MATERIAL WITH REAGENTS CONSISTING OFFROM 0.515% BY WEIGHT OF A PHENOL, FROM 1-25% BY WEIGHT OF A ZIRCONIUMSALT OF A VOLATILE ACID THE DISSOCIATION CONSTANT OF WHICH IS NOTGREATER THAN 5X10-3 AND THE BOILING POINT OF WHICH IS NOT HIGHER KTHAN160*C., THE BALANCE OF THE CELLULOSIC TEXTILE TREATING REAGENT BEING ALIQUID WHICH IS CHEMICALLY INERT WITH RESPECT TO CELLULOSE ANDCHEMICALLY INERT WITH RESPECT TO THE SAID REAGENTS AND DRYING THETREATED CELLULOSIC TEXTILE MATERIAL AT A TEMPERATURE OF FROM 70-170*C.